EP3120939B1 - Coated substrates, and their use and systems for the production of coated substrates - Google Patents

Description

The present invention relates to coated substrates and the use of these coated substrates.

Metallic and non-metallic components are often coated to create a smooth and/or shiny surface. As a rule, these are multi-layer coating systems. In addition to the desire to obtain a surface with a high-quality appearance, pronounced corrosion protection is also regularly sought with such coating systems. Permanent corrosion protection is often destroyed by mechanical damage. In many cases, even the slightest mechanical damage to coated surfaces will result in corrosion. In addition to discoloration, this can also result in infiltration phenomena. It is not uncommon for this to lead to the coating areas flaking off. There has been no lack of attempts to make coated shiny surfaces corrosion-resistant. For example be writes the DE 123 765 A1 a method for producing an anti-corrosion layer on a metallic surface, in which a sol based on silicon compounds, an aminoalkyl-functionalized alkoxysilane or a reaction product of the two components mentioned above is used.

According to the DE 38 33 119 C2 a corrosion-protected chromated metal surface that adheres very well to a substrate is obtained by depositing an electrophoretic paint directly onto the chromated layer without intermediate drying. '

the EP 2 752 504 relates to a method for producing a metallic or non-metallic metallically coated substrate, comprising the steps of: a) providing at least one substrate with at least one surface which can be metallically coatable at least in some areas; c) Application of at least one metallic composite protective layer containing at least one first metal selected from the group consisting of aluminum, manganese, magnesium and zinc as the main component, or at least one first metal alloy selected from the group consisting of steel, stainless steel, a magnesium alloy and a Aluminum alloy, and distributed in the main component present as a minor component at least one second metal and/or at least one oxidically bonded second metal selected from the group consisting of zirconium, titanium and hafnium, or consisting of the main component and the minor component, process step c ) comprises the partial steps: i) application of at least one metal layer containing or consisting of the at least one first metal or containing or consisting of the at least one first metal alloy by means of vapor deposition and/or sputtering technology on the coatable surface of the substrate and ii) treating the metal layer according to step i) with at least one first aqueous system containing at least one first compound of the second metal; d) silanizing the composite protective layer from step c) ii) by treatment with at least one second aqueous system to form at least one polysiloxane layer; and e) applying at least one lacquer layer to the polysiloxane layer according to step d). With this method one should arrive at coated substrates that are corrosion-resistant under mechanical stress or damage over a long period of time, which is characterized by a good Excellent adhesion of all layers and which retain an attractive appearance and show no signs of run-off or streaks.

From the EP 1 174 526 describes a process for the vapor deposition of several different metal vapors, such as zinc vapor and magnesium vapor, onto steel substrates under so-called throttled conditions, in which case the different metal vapors can also be mixed with one another before application. By applying the application under restricted conditions, it is said that two or more different metal vapors can be readily deposited on a substrate surface.

the EP 306 612 describes a method for applying layers to substrates, wherein layer material is converted into the gaseous state by means of at least two different devices in a vacuum chamber and deposited on the substrates to form a layer. In this case, a magnetic field-assisted cathode sputtering is carried out to convert a part of the material into vapor form and the conversion of another part of the material is effected by means of an electric arc discharge. On average over time, at least five atomic percent of the metal content to be applied to the functional surfaces of the substrates must come from the conversion of electrode material from the arc discharge into the vapor form. With this method, it should be possible to produce more compact, denser layers than has previously been possible using cathode sputtering.

In the U.S. 2014/295141 describes a coating process comprising the steps of depositing a layer of aluminum by evaporation on a surface of a semicrystalline polymer article and depositing a layer of hexamethyldisiloxane, also by evaporation, in a manner such that after heating the coated article to a temperature range of 165°C to 190 °C over a period of between one and four hours resulted in an aluminum layer with a thickness of less than 200 nm and a layer based on hexamethyldisiloxane with a thickness of less than 325 nm. The surface obtained in this way should be free of lines and be characterized by a diffuse reflection of not more than 2%, measured at 600 nm according to ASTM C1650-07. The result described is only obtained if an aluminum target with a Power density of 40 W/cm ² is sputtered for a maximum of two minutes and the object to be coated is passed in front of the aluminum target between two and 25 times. Gaseous hexamethyldisiloxane is then passed past the object to be coated for a period of between 1 and 20 seconds at a pressure of 20 to 75 mtorr. While the hexamethyldisiloxane is being passed, it is exposed to a power density in the range between 0.5 W/cm ² and 3 W/cm ² for a period of between 0.2 and 3.3 minutes. This process can be repeated 40 times.

the DE 198 59 695 A1 shows a method for coating substrates made of plastic with a light-reflecting layer, preferably an aluminum layer, and a further layer arranged between the substrate and the light-reflecting layer, the further layer being a highly crosslinked hydrocarbon, for example a silicon oxide, silicon nitride or Silicon oxynitride layer has a thickness of at least 15 nm and the plastic content of the barrier layer is < 15%.

the JP 5 298 189 B2 relates to a device comprising a vapor deposition chamber with an internal space that can be relieved of pressure, at least two vapor deposition sources in which the vapor deposition material is accommodated and which vaporize the vapor deposition material, a substrate that is arranged in the vapor deposition chamber, and a vapor injection nozzle with a mixing chamber and tubes in the form of flexible, pliable Tubing connecting the at least two vapor deposition sources and the vapor injection nozzle. Furthermore, this device comprises a heating element provided on the steam injection nozzle and on at least a portion of the tubes. The vapors mixed in the mixing chamber reach the vapor deposition chamber, in which the substrate to be coated is present, via the vapor injection nozzle. With the device according to JP 5 298 189 B2 It is said that various types of vapor deposition materials can be mixed and a homogeneous thin-film deposition film made of a composite material can be obtained.

However, anti-corrosion coatings for metal substrates still show considerable potential for improvement in terms of adhesion and corrosion protection, especially for mass-produced products, especially those with complex geometries.

The present invention was therefore based on the object of providing coated substrates which no longer have the disadvantages of the prior art and which, in particular, also in mass production provide coated products with improved corrosion protection and/or very good adhesion properties. Coated products are also sought which do not immediately show infiltration phenomena in the event of mechanical surface damage, in particular not associated with layers peeling off. Furthermore, the invention was based on the object of arriving at coated substrates which, even with complex geometry, show an equally high coating result over the entire component, including in the area of edge profiles.

1. a) Zurverfügungstellung eines nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, mit mindestens einer zumindest bereichsweise beschichtbaren Oberfläche,
2. b) Zurverfügungstellung einer Applikationsanlage für die Aufbringung einer Metallschicht, insbesondere Vakuumaufdampfanlage oder Sputter-Anlage,
3. c) Zurverfügungstellung mindestens eines Plasmagenerators und/oder mindestens einer Corona-Anlage, insbesondere in der Applikationsanlage für die Aufbringung einer Metallschicht, wie Vakuumaufdampfanlage oder Sputter-Anlage, oder als Bestandteil hiervon,
4. d) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung des nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, oder der beschichtbaren Oberfläche des nicht-metallischen Substrats, insbesondere Kunststoffsubstrats,
5. e) gegebenenfalls Behandeln des nach Schritt a) oder d) erhaltenen nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, oder der beschichtbaren Oberfläche des nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
6. f) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Polysiloxanschicht gemäß Schritt e),
7. g) gegebenenfalls Aufbringen mindestens einer Grundierungsschicht auf das nicht-metallische Substrat, insbesondere Kunststoffsubstrat, oder die beschichtbare Oberfläche des nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, gemäß Schritt a) oder d) oder auf die Polysiloxanschicht gemäß Schritt e) oder f),
8. h) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Grundierungsschicht gemäß Schritt g),
9. i) Behandeln des nach Schritt a) oder d) erhaltenen nicht-metallischen Substrats oder der beschichtbaren Oberfläche des nicht-metallischen Substrats oder der nach Schritt g) oder h) erhaltenen Grundierungsschicht mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
10. j) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Polysiloxanschicht gemäß Schritt i),
11. k) Aufbringen mindestens einer Metallschicht, enthaltend oder bestehend aus einem ersten Metall ausgewählt aus der Gruppe bestehend aus Aluminium, Silber, Gold, Blei, Vanadium, Mangan, Magnesium, Eisen, Kobalt, Nickel, Kupfer, Chrom, Palladium, Molybdän, Wolfram, Platin, Titan, Zirkonium und Zink, insbesondere Aluminium, oder enthaltend oder bestehend aus einer ersten Metalllegierung ausgewählt aus der Gruppe bestehend aus Messing, Bronze, Stahl, insbesondere Edelstahl, Alu minium-, Magnesium- und Titanlegierungen, mit der Applikationsanlage, insbesondere mittels Aufdampf- und/oder Sputter-Technik, auf das nicht-metallische Substrat, insbesondere Kunststoffsubstrat, oder auf die beschichtbare Oberfläche des nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, gemäß Schritt a) oder d) oder auf die Polysiloxanschicht gemäß Schritt e) oder f) oder auf die Grundierungsschicht gemäß Schritt g) oder h) oder auf die Polysiloxanschicht gemäß Schritt i) oder j),
12. l) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Metallschicht gemäß Schritt k),
13. m) Behandeln der nach Schritt k) oder 1) erhaltenen Metallschicht mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
14. n) Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Polysiloxanschicht gemäß Schritt m) und
15. o) Auftragen einer, insbesondere transparenten, Deckschicht auf die behandelte Polysiloxanschicht gemäß Schritt n).

Accordingly, a coated non-metallic substrate was obtained or found to be obtainable by a method for producing a coated non-metallic substrate, in particular a plastic substrate, comprising the steps

1. a) Provision of a non-metallic substrate, in particular a plastic substrate, with at least one surface that can be coated at least in certain areas,
2. b) Provision of an application system for the application of a metal layer, in particular a vacuum vapor deposition system or sputter system,
3. c) Provision of at least one plasma generator and/or at least one corona system, in particular in the application system for the application of a metal layer, such as a vacuum vapor deposition system or sputter system, or as a component thereof,
4. d) optionally plasma treatment with the plasma generator and/or corona treatment of the non-metallic substrate, in particular plastic substrate, or the coatable surface of the non-metallic substrate, in particular plastic substrate,
5. e) optionally treating the non-metallic substrate obtained after step a) or d), in particular plastic substrate, or the coatable surface of the non-metallic substrate, in particular plastic substrate, with at least one organosilicon compound, in particular by means of plasma polymerization, to form a polysiloxane layer,
6. f) optionally plasma treatment with the plasma generator and/or corona treatment of the polysiloxane layer according to step e),
7. g) optionally applying at least one primer layer to the non-metallic substrate, in particular plastic substrate, or the coatable surface of the non-metallic substrate, in particular plastic substrate, according to step a) or d) or to the polysiloxane layer according to step e) or f),
8. h) optionally plasma treatment with the plasma generator and/or corona treatment of the primer layer according to step g),
9. i) treating the non-metallic substrate obtained after step a) or d) or the coatable surface of the non-metallic substrate or the primer layer obtained after step g) or h) with at least one organosilicon compound, in particular by means of plasma polymerization, to form a polysiloxane layer ,
10. j) optionally plasma treatment with the plasma generator and/or corona treatment of the polysiloxane layer according to step i),
11. k) Application of at least one metal layer containing or consisting of a first metal selected from the group consisting of aluminum, silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt, nickel, copper, chromium, palladium, molybdenum, tungsten, platinum, titanium, zirconium and zinc, especially aluminium, or containing or consisting of a first metal alloy selected from the group consisting of brass, bronze, steel, in particular stainless steel, aluminum minium, magnesium and titanium alloys, with the application system, in particular by means of vapor deposition and/or sputtering technology, on the non-metallic substrate, in particular plastic substrate, or on the coatable surface of the non-metallic substrate, in particular plastic substrate, according to step a ) or d) or on the polysiloxane layer according to step e) or f) or on the primer layer according to step g) or h) or on the polysiloxane layer according to step i) or j),
12. l) optionally plasma treatment with the plasma generator and/or corona treatment of the metal layer according to step k),
13. m) treating the metal layer obtained after step k) or 1) with at least one organosilicon compound, in particular by means of plasma polymerization, to form a polysiloxane layer,
14. n) plasma treatment with the plasma generator and/or corona treatment of the polysiloxane layer according to step m) and
15. o) Application of a cover layer, in particular a transparent one, to the treated polysiloxane layer according to step n).

• a) Zurverfügungstellung eines nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, mit mindestens einer zumindest bereichsweise beschichtbaren Oberfläche,
• b) Zurverfügungstellung einer Applikationsanlage für die Aufbringung einer Metallschicht, insbesondere Vakuumaufdampfanlage oder Sputter-Anlage,
• c) Zurverfügungstellung mindestens eines Plasmagenerators und/oder mindestens einer Corona-Anlage, insbesondere in der Applikationsanlage für die Aufbringung einer Metallschicht, wie Vakuumaufdampfanlage oder Sputter-Anlage, oder als Bestandteil hiervon,
• d) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung des nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, oder der beschichtbaren Oberfläche des nicht-metallischen Substrats, insbesondere Kunststoffsubstrats,
• e) gegebenenfalls Behandeln des nach Schritt a) oder d) erhaltenen nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, oder der beschichtbaren Oberfläche des nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
• f) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Polysiloxanschicht gemäß Schritt e),
• g) Aufbringen mindestens einer Grundierungsschicht auf das nicht-metallische Substrat, insbesondere Kunststoffsubstrat, oder die beschichtbare Oberfläche des nicht-metallischen Substrats, insbesondere Kunststoffsubstrats, gemäß Schritt a) oder d) oder auf die Polysiloxanschicht gemäß Schritt e) oder f),
• h) Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Grundierungsschicht gemäß Schritt g),
• i) Behandeln des nach Schritt a) oder d) erhaltenen nicht-metallischen Substrats oder der beschichtbaren Oberfläche des nicht-metallischen Substrats oder der nach Schritt g) oder h) erhaltenen Grundierungsschicht mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
• k) Aufbringen mindestens einer Metallschicht, enthaltend oder bestehend aus einem ersten Metall ausgewählt aus der Gruppe bestehend aus Aluminium, Silber, Gold, Blei, Vanadium, Mangan, Magnesium, Eisen, Kobalt, Nickel, Kupfer, Chrom, Palladium, Molybdän, Wolfram, Platin, Titan, Zirkonium und Zink, insbesondere Aluminium, oder enthaltend oder bestehend aus einer ersten Metalllegierung ausgewählt aus der Gruppe bestehend aus Messing, Bronze, Stahl, insbesondere Edelstahl, Aluminium-, Magnesium- und Titanlegierungen, mit der Applikationsanlage, insbesondere mittels Aufdampf- und/oder Sputter-Technik, auf die Grundierungsschicht gemäß Schritt g) oder h) oder auf die Polysiloxanschicht gemäß Schritt i),
• m) Behandeln der nach Schritt k) erhaltenen Metallschicht mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
• n) Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Polysiloxanschicht gemäß Schritt m) und
• o) Auftragen einer, insbesondere transparenten, Deckschicht auf die behandelte Polysiloxanschicht gemäß Schritt n).

The object on which the invention is based is also achieved in particular by a coated non-metallic substrate, obtained or obtainable by a method comprising the steps

• a) Provision of a non-metallic substrate, in particular a plastic substrate, with at least one surface that can be coated at least in certain areas,
• b) Provision of an application system for the application of a metal layer, in particular a vacuum vapor deposition system or sputter system,
• c) Provision of at least one plasma generator and/or at least one corona system, in particular in the application system for the application of a metal layer, such as a vacuum vapor deposition system or sputter system, or as a component thereof,
• d) optionally plasma treatment with the plasma generator and/or corona treatment of the non-metallic substrate, in particular the plastic substrate, or the coatable surface of the non-metallic substrate, in particular a plastic substrate,
• e) optionally treating the non-metallic substrate obtained after step a) or d), in particular plastic substrate, or the coatable surface of the non-metallic substrate, in particular plastic substrate, with at least one organosilicon compound, in particular by means of plasma polymerization, to form a polysiloxane layer,
• f) optionally plasma treatment with the plasma generator and/or corona treatment of the polysiloxane layer according to step e),
• g) Application of at least one primer layer to the non-metallic substrate, in particular plastic substrate, or the coatable surface of the non-metallic substrate, in particular plastic substrate, according to step a) or d) or to the polysiloxane layer according to step e) or f),
• h) plasma treatment with the plasma generator and/or corona treatment of the primer layer according to step g),
• i) treating the non-metallic substrate obtained after step a) or d) or the coatable surface of the non-metallic substrate or the primer layer obtained after step g) or h) with at least one organosilicon compound, in particular by means of plasma polymerization, to form a polysiloxane layer ,
• k) Application of at least one metal layer containing or consisting of a first metal selected from the group consisting of aluminum, silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt, nickel, copper, chromium, palladium, molybdenum, tungsten, Platinum, titanium, zirconium and zinc, in particular aluminium, or containing or consisting of a first metal alloy selected from the group consisting of brass, bronze, steel, in particular stainless steel, aluminium, magnesium and titanium alloys, with the application system, in particular by means of vapor deposition and/or sputtering technique, on the primer layer according to step g) or h) or on the polysiloxane layer according to step i),
• m) treating the metal layer obtained after step k) with at least one organosilicon compound, in particular by means of plasma polymerization, to form a polysiloxane layer,
• n) plasma treatment with the plasma generator and/or corona treatment of the polysiloxane layer according to step m) and
• o) Application of a cover layer, in particular a transparent one, to the treated polysiloxane layer according to step n).

In this process variant, steps d), e) and f) are only optional. In individual cases, they can contribute to improved adhesion and increased protection against corrosion. The same applies to step i). It has been shown that it is advantageous if a polysiloxane layer, in particular a plasma-generated one, is present on both sides of the metal layer and has preferably been subjected to a plasma treatment and/or a corona treatment, in particular a plasma treatment.

The variant of the method described above, including the application of a primer layer, is particularly useful for non-metallic substrates, in particular plastic substrates, with a surface that has unevenness or is of inferior quality.

For many applications, however, such a method has proven to be completely sufficient to solve the objects on which the invention is based, which, in addition to method steps a), b) and c), also includes method steps d), e), f), i) , k), m), n) and o) or i), k), m), n) and o) as mandatory process steps, each prior to the step of applying the metal layer k) the application of a, in particular plasma-generated , Polysiloxane layer (step i)) is provided. The variant of the method described above can be used in particular with perfect non-metallic substrates, in particular plastic substrates with a perfect or smooth surface.

Furthermore, in a further development of the method described herein for the production of non-metallic substrates according to the invention, in particular plastic substrates, use can be made of adhering to the sequence of steps d), e), f), g), i), k), m) , n) and o) or g), i), k), m), n) and o), ie without treating or activating the primer layer with a plasma (step h)). Nevertheless, step h) can also be used here. Here, too, it is advantageous to apply a polysiloxane layer, in particular a plasma-generated one, before the step of applying the metal layer k) (step i)). Furthermore, in one embodiment, in addition to method steps a), b) and c), on the sequence of process steps d), e), f), g), h), i), k), m), n) and o) or process steps d), j), k), m), n ) and o) are made use of.

In a particularly expedient embodiment, in particular as specified above, the layer to which the metal layer is applied according to step k) is subjected to a plasma treatment with the plasma generator and/or a corona treatment before step k) (e.g. step j), f) or d)).

It has proven to be advantageous to have the method steps mentioned above essentially follow one another directly. In particular, this means that prolonged storage after the plasma treatment steps should be avoided. Rather, it is advantageous if the subsequent method step follows directly. It has also been shown that, in addition to the method steps mentioned above, it is not necessary to interpose further method steps.

In a preferred embodiment, it has also proven to be favorable, in particular with regard to good adhesion and corrosion protection, if the non-metallic substrate, in particular the plastic substrate, is subjected to a plasma treatment and/or corona treatment, in particular plasma treatment (step d)) .

Suitable non-metallic substrates include glass, ceramic, composite fiber materials, carbon materials, plastic, or wood. The process described here is particularly well suited for the coating of plastic substrates in order to obtain permanently high-gloss products. Suitable plastic substrates include or consist, for example, of PVC, polyurethanes, polyacrylates, polyesters, e.g. PBT and PET, polyolefins, in particular polypropylene, polycarbonates, polyamides, polyphenylene ethers, polystyrene, styrene (co)polymers such as ABS, SAN, ASA or MABS, polyoxyalkylene, e.g. POM, Teflon and polymer blends, in particular ABS/PPE, ASA/PPE, SAN/PPE and/or ABS/PC blends.

1. A) Zurverfügungstellung eines Metallsubstrats mit mindestens einer zumindest bereichsweise beschichtbaren Oberfläche,
2. B) Zurverfügungstellung einer Applikationsanlage für die Aufbringung einer Metallschicht, insbesondere Vakuumaufdampfanlage,
3. C) Zurverfügungstellung mindestens eines Plasmagenerators und/oder mindestens einer Corona-Anlage, insbesondere in der Applikationsanlage für die Aufbringung einer Metallschicht, wie Vakuumaufdampfanlage oder der Sputter-Anlage, oder als Bestandteil hiervon,
4. D) gegebenenfalls Reinigung des Metallsubstrats oder der beschichtbaren Oberfläche des Metallsubstrats,
5. E) gegebenenfalls Aufbringen mindestens einer Metallschicht, enthaltend oder bestehend aus einem zweiten Metall ausgewählt aus der Gruppe bestehend aus Titan, Hafnium und Zirkonium, insbesondere Zirkonium, oder aus einer zweiten Metalllegierung ausgewählt aus der Gruppe bestehend aus Titan-, Hafnium- und Zirkoniumlegierungen, mit der Applikationsanlage, insbesondere mittels Aufdampf- und/oder Sputter-Technik, auf das Metallsubstrat oder die beschichtbare Oberfläche des Metallsubstrats gemäß Schritt A) oder D),
6. F) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung des Metallsubstrats oder der beschichtbaren Oberfläche des Metallsubstrats gemäß Schritt A) oder D) oder der Metallschicht gemäß Schritt E),
7. G) gegebenenfalls Behandeln des nach Schritt A) oder D) erhaltenen Metallsubstrats oder Behandeln der nach Schritt A) oder D) erhaltenen beschichtbaren Oberfläche des Metallsubstrats oder der nach Schritt E) oder F) erhaltenen Metallschicht mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
8. H) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Polysiloxanschicht gemäß Schritt G),
9. I) gegebenenfalls Aufbringen einer Konversionsschicht auf das Metallsubstrat oder die beschichtbare Oberfläche des Metallsubstrats gemäß Schritt A) oder D) oder auf die Metallschicht gemäß Schritt E) oder F) oder auf die Polysiloxanschicht gemäß Schritt G) oder H),
10. J) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Konversionsschicht gemäß Schritt I),
11. K) gegebenenfalls Behandeln der nach Schritt I) oder J) erhaltenen Konversionsschicht mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
12. L) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der nach Schritt K) erhaltenen behandelten Polysiloxanschicht,
13. M) gegebenenfalls Aufbringen mindestens einer Grundierungsschicht auf das Metallsubstrat oder die beschichtbare Oberfläche des Metallsubstrats gemäß Schritt A) oder D) oder auf die Metallschicht gemäß Schritt E) oder F) oder auf die Polysiloxanschicht gemäß Schritt G) oder H) oder auf die Konversionsschicht gemäß Schritt I) oder J) oder auf die Polysiloxanschicht gemäß Schritt K) oder L),
14. N) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Grundierungsschicht gemäß Schritt M),
15. O) Behandeln des nach Schritt A) oder D) erhaltenen Metallsubstrats oder Behandeln der nach Schritt A) oder D) erhaltenen beschichtbaren Oberfläche des Metallsubstrats oder der nach Schritt E) oder F) erhaltenen Metallschicht oder der nach Schritt I) oder J) erhaltenen Konversionsschicht oder der nach Schritt M) oder N) erhaltenen Grundierungsschicht mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
16. P) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der nach Schritt O) erhaltenen behandelten Polysiloxanschicht,
17. Q) Aufbringen mindestens einer Metallschicht, enthaltend oder bestehend aus einem ersten Metall ausgewählt aus der Gruppe bestehend aus Aluminium, Silber, Gold, Blei, Vanadium, Mangan, Magnesium, Eisen, Kobalt, Molybdän, Wolfram, Nickel, Kupfer, Chrom, Palladium, Platin, Titan, Zirkonium und Zink, insbesondere Aluminium, oder enthaltend oder bestehend aus einer ersten Metalllegierung ausgewählt aus der Gruppe bestehend aus Messing, Bronze, Stahl, insbesondere Edelstahl, Aluminium-, Magnesium- und Titanlegierungen, mit der Applikationsanlage, insbesondere mittels Aufdampf- und/oder Sputter-Technik, auf das Metallsubstrat oder die beschichtbare Oberfläche des Metallsubstrats gemäß Schritt A) oder D) oder F) auf oder die Polysiloxanschicht gemäß Schritt G) oder H) oder auf die Konversionsschicht gemäß Schritt I) oder J) oder auf die Polysiloxanschicht gemäß Schritt K) oder L) oder auf die Grundierungsschicht gemäß Schritt M) oder N) oder auf die Polysiloxanschicht gemäß Schritt O) oder P),
18. R) gegebenenfalls Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Metallschicht gemäß Schritt Q),
19. S) Behandeln der nach Schritt Q) oder R) erhaltenen Metallschicht mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
20. T) Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Polysiloxanschicht gemäß Schritt S) und
21. U) Auftragen einer, insbesondere transparenten, Deckschicht auf die behandelte Polysiloxanschicht gemäß Schritt T).

The object on which the invention is based is furthermore achieved by a coated metal substrate obtained or obtainable by a method for producing a coated metal substrate, comprising

1. A) Provision of a metal substrate with at least one surface that can be coated at least in certain areas,
2. B) Provision of an application system for the application of a metal layer, in particular a vacuum vapor deposition system,
3. C) Provision of at least one plasma generator and/or at least one corona system, in particular in the application system for the application of a metal layer, such as a vacuum vapor deposition system or the sputter system, or as a component thereof,
4. D) optionally cleaning the metal substrate or the coatable surface of the metal substrate,
5. E) optionally applying at least one metal layer containing or consisting of a second metal selected from the group consisting of titanium, hafnium and zirconium, in particular zirconium, or a second metal alloy selected from the group consisting of titanium, hafnium and zirconium alloys, with the application system, in particular by means of vapor deposition and/or sputtering technology, onto the metal substrate or the coatable surface of the metal substrate according to step A) or D),
6. F) optionally plasma treatment with the plasma generator and/or corona treatment of the metal substrate or the coatable surface of the metal substrate according to step A) or D) or the metal layer according to step E),
7. G) optionally treating the metal substrate obtained according to step A) or D) or treating the coatable surface of the metal substrate obtained according to step A) or D) or the metal layer obtained according to step E) or F) with at least one organosilicon compound, in particular by means of plasma polymerization, with the formation of a polysiloxane layer,
8. H) optionally plasma treatment with the plasma generator and/or corona treatment of the polysiloxane layer according to step G),
9. I) optionally applying a conversion layer to the metal substrate or the coatable surface of the metal substrate according to step A) or D) or to the metal layer according to step E) or F) or to the polysiloxane layer according to step G) or H),
10. J) optionally plasma treatment with the plasma generator and/or corona treatment of the conversion layer according to step I),
11. K) optionally treating the conversion layer obtained after step I) or J) with at least one organosilicon compound, in particular by means of plasma polymerization, to form a polysiloxane layer,
12. L) optionally plasma treatment with the plasma generator and/or corona treatment of the treated polysiloxane layer obtained after step K),
13. M) optionally applying at least one primer layer to the metal substrate or the coatable surface of the metal substrate according to step A) or D) or to the metal layer according to step E) or F) or to the polysiloxane layer according to step G) or H) or to the conversion layer according to Step I) or J) or on the polysiloxane layer according to step K) or L),
14. N) optionally plasma treatment with the plasma generator and/or corona treatment of the primer layer according to step M),
15. O) treating the metal substrate obtained after step A) or D) or treating the coatable surface of the metal substrate obtained after step A) or D) or the metal layer obtained after step E) or F) or the conversion layer obtained after step I) or J). or the primer layer obtained after step M) or N) with at least one organosilicon compound, in particular by means of plasma polymerisation, to form a polysiloxane layer,
16. P) optionally plasma treatment with the plasma generator and/or corona treatment of the treated polysiloxane layer obtained after step O),
17. Q) Application of at least one metal layer containing or consisting of a first metal selected from the group consisting of aluminum, silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt, molybdenum, tungsten, nickel, copper, chromium, palladium, Platinum, titanium, zirconium and zinc, in particular aluminium, or containing or consisting of a first metal alloy selected from the group consisting of brass, bronze, steel, in particular stainless steel, aluminium, magnesium and titanium alloys, with the application system, in particular by means of vapor deposition and/or sputtering technique, onto the metal substrate or the coatable surface of the metal substrate according to step A) or D) or F) or onto the polysiloxane layer according to step G) or H) or onto the conversion layer according to step I) or J) or on the polysiloxane layer according to step K) or L) or on the primer layer according to step M) or N) or on the polysiloxane layer according to step O) or P),
18. R) optionally plasma treatment with the plasma generator and/or corona treatment of the metal layer according to step Q),
19. S) treating the metal layer obtained after step Q) or R) with at least one organosilicon compound, in particular by means of plasma polymerization, to form a polysiloxane layer,
20. T) plasma treatment with the plasma generator and/or corona treatment of the polysiloxane layer according to step S) and
21. U) Application of a cover layer, in particular a transparent one, to the treated polysiloxane layer according to step T).

• A) Zurverfügungstellung eines Metallsubstrats mit mindestens einer zumindest bereichsweise beschichtbaren Oberfläche,
• B) Zurverfügungstellung einer Applikationsanlage für die Aufbringung einer Metallschicht, insbesondere Vakuumaufdampfanlage,
• C) Zurverfügungstellung mindestens eines Plasmagenerators und/oder mindestens einer Corona-Anlage, insbesondere in der Applikationsanlage für die Aufbringung einer Metallschicht, wie Vakuumaufdampfanlage oder der Sputter-Anlage, oder als Bestandteil hiervon,
• D) Reinigung des Metallsubstrats oder der beschichtbaren Oberfläche des Metallsubstrats,
• M) Aufbringen mindestens einer Grundierungsschicht auf das Metallsubstrat oder die beschichtbare Oberfläche des Metallsubstrats gemäß Schritt D),
• O) Behandeln des nach Schritt A) oder D) erhaltenen Metallsubstrats oder Behandeln der nach Schritt A) oder D) erhaltenen beschichtbaren Oberfläche des Metallsubstrats oder der nach Schritt E) oder F) erhaltenen Metallschicht oder der nach Schritt I) oder J) erhaltenen Konversionsschicht oder der nach Schritt M) oder N) erhaltenen Grundierungsschicht mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
• Q) Aufbringen mindestens einer Metallschicht, enthaltend oder bestehend aus einem ersten Metall ausgewählt aus der Gruppe bestehend aus Aluminium, Silber, Gold, Blei, Vanadium, Mangan, Magnesium, Eisen, Kobalt, Molybdän, Wolfram, Nickel, Kupfer, Chrom, Palladium, Platin, Titan, Zirkonium und Zink, insbesondere Aluminium, oder enthaltend oder bestehend aus einer ersten Metalllegierung ausgewählt aus der Gruppe bestehend aus Messing, Bronze, Stahl, insbesondere Edelstahl, Aluminium-, Magnesium- und Titanlegierungen, mit der Applikationsanlage, insbesondere mittels Aufdampf- und/oder Sputter-Technik, auf die Grundierungsschicht gemäß Schritt M),
• S) Behandeln der nach Schritt Q) erhaltenen Metallschicht mit mindestens einer siliziumorganischen Verbindung, insbesondere mittels Plasmapolymerisation, unter Ausbildung einer Polysiloxanschicht,
• T) Plasmabehandlung mit dem Plasmagenerator und/oder Corona-Behandlung der Polysiloxanschicht gemäß Schritt S) und
• U) Auftragen einer, insbesondere transparenten, Deckschicht auf die Polysiloxanschicht gemäß Schritt T).

The object on which the invention is based is also achieved in particular by a coated metallic substrate, obtained or obtainable by such a method, comprising the steps

• A) Provision of a metal substrate with at least one surface that can be coated at least in certain areas,
• B) Provision of an application system for the application of a metal layer, in particular a vacuum vapor deposition system,
• C) Provision of at least one plasma generator and/or at least one corona system, in particular in the application system for the application of a metal layer, such as a vacuum vapor deposition system or the sputter system, or as a component thereof,
• D) cleaning of the metal substrate or the coatable surface of the metal substrate,
• M) applying at least one primer layer to the metal substrate or the coatable surface of the metal substrate according to step D),
• O) treating the metal substrate obtained after step A) or D) or treating the coatable surface of the metal substrate obtained after step A) or D) or the metal layer obtained after step E) or F) or the conversion layer obtained after step I) or J). or the primer layer obtained after step M) or N) with at least one organosilicon compound, in particular by means of plasma polymerisation, to form a polysiloxane layer,
• Q) Application of at least one metal layer containing or consisting of a first metal selected from the group consisting of aluminum, silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt, molybdenum, tungsten, nickel, copper, chromium, palladium, Platinum, titanium, zirconium and zinc, in particular aluminum, or containing or consisting of a first metal alloy selected from the group consisting of brass, bronze, steel, in particular stainless steel, aluminium, magnesium and titanium alloys, with the application system, in particular by means of vapor deposition and/or sputtering technology, onto the primer layer according to step M),
• S) treating the metal layer obtained after step Q) with at least one organosilicon compound, in particular by means of plasma polymerization, to form a polysiloxane layer,
• T) plasma treatment with the plasma generator and/or corona treatment of the polysiloxane layer according to step S) and
• U) Application of a cover layer, in particular a transparent one, to the polysiloxane layer according to step T).

It has been shown that it is also advantageous in the production of coated metal substrates if there is a polysiloxane layer, in particular plasma-polymerized, on both sides of the metal layer, preferably with subsequent plasma treatment and/or corona treatment, in particular plasma treatment. Thus, for example, the method variant described above can also be equipped with step O).

A particularly pronounced protection against corrosion is also obtained with the metal substrate obtainable by the method described herein by applying at least one metal layer containing or consisting of a second metal selected from the group to the metal substrate cleaned according to step D) or the cleaned coatable surface of the metal substrate consisting of titanium, hafnium and zirconium, in particular zirconium, or from a second metal alloy selected from the group consisting of titanium, hafnium and zirconium alloys, applied with the application system, in particular by means of vapor deposition and/or sputtering technology (step E) ). It is particularly advantageous here if this metal layer is subsequently subjected to a plasma treatment step (step F)).

In addition to process steps A) to C), process steps D), G), H), M), O), Q), S), T) and U) can also be provided as mandatory process steps for the production of coated metal substrates to fall back.

In addition, the method described herein delivers by following the sequence of the mandatory method steps D), E), G), H), M), O), Q), S), T) and U) or by following the sequence of the mandatory Process steps D), M), N), O), Q), S), T) and U) or in compliance with the sequence of mandatory process steps D), G), H), O), Q), S), T) and U) very satisfactory results in terms of adhesion, gloss and corrosion resistance, particularly when the process steps follow one another directly in the order mentioned.

The following process sequence is also very expedient, in which, in addition to process steps A) to C), use is made of the sequence D), I), K), L), O), Q), S), T) and U) or from the sequence D), F), O), Q), S), T) and U) or from the sequence D), G), H), O), Q), S), T) and U ).

In a particularly useful embodiment, the layer to which the metal layer is applied according to step Q) is subjected to a plasma treatment with the plasma generator and/or a corona treatment (for example steps P), N), L) before step Q). J), H), F) or D)). This also applies in particular to the polysiloxane layer.

In a preferred embodiment, it has also proven to be advantageous, in particular with regard to good adhesion and corrosion protection, if the metallic substrate, in particular the cleaned metallic substrate, is subjected to a plasma treatment and/or corona treatment, in particular plasma treatment (step F)) .

It has therefore often proven to be advantageous if, when a polysiloxane layer is applied, this layer is then subjected to a plasma treatment and/or a corona treatment, in particular a plasma treatment. The same applies to the application of a primer layer. Here, too, it has proven advantageous first subjecting the primer layer obtained to a plasma treatment and/or a corona treatment, in particular a plasma treatment.

Accordingly, it has also proven to be advantageous in the production of coated metal substrates by the method described herein to have the previously mentioned method steps essentially follow one another directly. In particular, this means that prolonged storage after the plasma treatment steps should be avoided. Rather, it is advantageous if the subsequent method step follows directly. It has also been shown that, in addition to the method steps mentioned above, it is not necessary to interpose further method steps.

Metals and metal alloys can be used for the metal substrates, with particularly suitable metal substrates being able to be selected from the group consisting of aluminum, aluminum alloys, iron, iron alloys, in particular steel or stainless steel, copper, copper alloys, titanium, titanium alloys, zinc, zinc alloys, nickel, Nickle alloys, molybdenum, molybdenum alloys, magnesium, magnesium alloys, lead, lead alloys, tungsten, tungsten alloys, manganese, manganese alloys, brass, bronze, die-cast nickel, die-cast zinc and die-cast aluminum or any mixtures thereof.

Suitable methods for cleaning metal substrates are known to those skilled in the art. Such cleaning processes (step D)) include degreasing, pickling, phosphating, in particular iron and/or zinc phosphating, polishing, grinding, in particular vibratory grinding, and/or treating with dry ice. These methods can be used individually or in any combination. For many applications it has proved to be sufficient to clean the metal substrates by treating them with dry ice. When cleaning with dry ice, dry ice particles in the form of pellets or in the form of crystals, which have been scraped off a corresponding block of dry ice, are generally accelerated with the aid of compressed air and directed onto the metal surface to be cleaned. The cleaning effect is said to be due to thermal, kinetic and phase change effects. Devices and methods for cleaning of metal surfaces with dry ice are for example the DE 195 44 906 A1 and EP 2 886 250 refer to.

For example, the surface of metal substrates can be degreased with alkaline or acidic reagents. Commercial degreasing steps are also known by the terms boiling or pickling degreasing. Alternatively, a metal surface can be anodically degreased in an electrolytic degreasing bath.

For some design variants, it is advantageous to subject the, in particular degreased, metal substrate surface to at least one pickling step. An acidic rinsing bath, for example, is used to pickle the metal substrate surface. A suitable pickling solution is, for example, dilute hydrochloric acid (1:10 vol/vol). Like the degreasing step, the pickling step is generally completed by a rinsing step. If the metal substrate surface is polished and/or ground or tumbled, the degreasing and/or pickling step can often be omitted. With this type of surface treatment, sufficient material is usually removed from this surface, with the result that impurities or other components lying on or adhering to the surface are also removed. If the surface is polished or ground, it is also often possible to dispense with the application of a first and optionally a second primer layer. Such an even or smooth surface is usually obtained by polishing or grinding that smoothing by applying a primer layer is no longer necessary. However, if the metal substrate has numerous nooks and crannies that cannot be readily polished or ground sufficiently, it may be advisable to add a first and possibly a second priming step.

Subsequent to or instead of the degreasing step, the metallic substrate surface can be phosphated and/or passivated. This is particularly preferred in the case of substrates made of or containing aluminum.

In a further embodiment of the method described here for the production of coated metal substrates, very particularly corrosion-resistant substrates are obtained in that, in the step of applying the metal layer, a first metal, in particular aluminum, or a first metal alloy, in particular an aluminum alloy, is used in the application system for the Application of a metal layer, in particular the vacuum vapor deposition system or the sputter system, overlapping in time with a second metal that is different from the first metal, in particular selected from the group consisting of titanium, zirconium and hafnium, in particular zirconium, or with a second metal alloy, in particular a zirconium alloy different from the first metal alloy is co-evaporated. This is achieved, for example, by placing metal pellets or rods of the first metal or metal alloy in a corresponding first receptacle, in particular a first boat or a first coil, and placing the metal pellets or rods of the second metal or metal alloy in a corresponding second receptacle, second boat or a second coil, and that the first and the second receptacle are heated in such a way that the melting points of the first and second metal or first and second metal alloy or of the first metal and second metal alloy or , achieved and/or maintained by the first metal alloy and the second metal substantially simultaneously or within an overlapping period of time.

The person skilled in the art is familiar with suitable aqueous conversion systems with the aid of which conversion layers are obtained. As an example, refer to the revelations of U.S. 2,825,697 and U.S. 2,928,763 referred.

Methods which are well known to those skilled in the art are available for applying the primer layer. Examples include the wet paint process, the powder coating process or application using UV-curing coating systems. Accordingly, in a preferred embodiment, the primer layer can be based on, in particular UV-curing, powdered polyester resin compounds or on epoxy/polyester powder. Of course it is also possible, before applying a primer layer, as described above, to mechanically smooth the metal substrate surface, for example by means of grinding and/or polishing or vibratory grinding.

Suitable organosilicon compounds are known to those skilled in the art. In an expedient embodiment, at least one amino-containing silane is used for this purpose, in particular aminopropyltriethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane or any mixtures thereof. Hexamethyldisiloxane and tetramethyldisiloxane are particularly preferably used, hexamethyldisiloxane being regularly particularly suitable.

m

0, 1, 2 oder 3, insbesondere 2 oder 3,

R1

C1- bis C10-Kohlenwasserstoffrest, insbesondere eine C1- bis C10-Kohlenwasserstoffkette, die durch Sauerstoff oder Stickstoff unterbrochen sein kann, insbesondere Methyl, Ethyl oder i- oder n-Propyl, vorzugsweise i- oder n-Propyl,

R2

gleiche oder verschiedene hydrolysierbare Gruppen, insbesondere Alkoxygruppen wie Methoxy-, Ethoxy-, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy oder t-Butoxy, insbesondere Methoxy oder Ethoxy,

R3

gleiche oder verschiedene C1 - bis C5-Alkylgruppen, insbesondere Methyl, Ethyl oder i- oder n-Propyl, vorzugsweise i- oder n-Propyl,

X

funktionelle polymerisierbare Gruppe, insbesondere ein in ω-Stellung ungesättigter organischer Rest wie eine in ω-Stellung ungesättigte Alkenylgruppe mit 1 bis 10, vorzugsweise 2 bis 4 C-Atomen oder ein in ω-Stellung ungesättigter Carbonsäureesterrest von Carbonsäuren mit bis zu 4 Kohlenstoffatomen und Alkoholen mit bis zu 6 Kohlenstoffatomen.

Suitable organosilicon compounds also include, as monomer or comonomer building blocks, compounds of the following formula (1):

XR ₁ -Si(R ₂ ) _3-m (R ₃ ) _m (I),

where the substituents and indices have the following meanings:

m

0, 1, 2 or 3, in particular 2 or 3,

R1

C1 to C10 hydrocarbon radical, in particular a C1 to C10 hydrocarbon chain which can be interrupted by oxygen or nitrogen, in particular methyl, ethyl or i- or n-propyl, preferably i- or n-propyl,

R2

identical or different hydrolyzable groups, in particular alkoxy groups such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy or t-butoxy, in particular methoxy or ethoxy,

R3

identical or different C1 - to C5-alkyl groups, in particular methyl, ethyl or i- or n-propyl, preferably i- or n-propyl,

X

functional polymerizable group, in particular an ω-unsaturated organic radical such as an ω-unsaturated alkenyl group having 1 to 10, preferably 2 to 4 carbon atoms or an ω-unsaturated carboxylic acid ester radical of carboxylic acids having up to 4 carbon atoms and alcohols with up to 6 carbon atoms.

Particularly suitable radicals X include, for example, vinyl, alkylvinyl, especially methyl, ethyl or propylvinyl, (meth)acryloxyalkyl, especially (meth)acryloxymethyl, (meth)acryloxyethylene or (meth)acryloxypropyl, especially (meth)acryloxypropyl. In a further development of the method described here, it is provided that a first organosilicon compound is supplied via a supply line from a first container of this application system, in particular vacuum chamber, located outside the application system for the application of a metal layer, in particular outside the vacuum chamber of the vacuum vapor deposition system, and that a second organosilicon compound, which differs from the first organosilicon compound, is supplied via a feed line from a second container located outside the application system for the application of a metal layer, in particular outside the vacuum chamber of the vacuum vapor deposition system, of this application system, in particular vacuum chamber. Alternatively, the same organosilicon compound can also be present in the first and the second container. In particular, it is possible that even when the same organosilicon compounds are used, one of these organosilicon compounds can be mixed with another, different organosilicon compound and/or with a colorant, in particular a dye. Accordingly, the methods described herein are also characterized in that at least one colorant, in particular a dye, is introduced into the application system for the application of a metal layer, preferably in the form of a mixture, together with the at least one organosilicon compound, in particular for the plasma polymerization . The last-mentioned variant of the method, comprising the use of a colorant, is of course also successful when only one container is used.

Accordingly, the present disclosure also refers to an application system for the application of a metal layer comprising at least one first container, in particular outside the application system for the application of a metal layer, in particular outside the vacuum chamber of the vacuum vapor deposition system, for receiving a first silicon-organic compound with a feed line the application system, in particular to the vacuum chamber, and at least a second, in particular outside the application system for the application of a metal layer, in particular Outside the vacuum chamber of the vacuum vapor deposition system, present container for receiving a second organosilicon compound with a feed line to the application system, in particular to the vacuum chamber.

Particularly good adhesion without restrictions in terms of corrosion resistance is also obtained in particular by the step of treatment with at least one organosilicon compound such as hexamethyldisiloxane, in particular by means of plasma polymerisation, with the formation of a polysiloxane layer in the presence of at least one reactive gas such as oxygen, nitrogen, carbon dioxide, hydrogen , carbon monoxide, hydrogen peroxide gas, water vapor, ozone and/or air, in particular in the presence of oxygen or air. The incorporation of reactive gases, in particular air or oxygen, in the, in particular plasma-generated, polymerization process results in harder polysiloxane layers than in the conventional production of such polysiloxane layers without the use of the reactive gases described. These harder polysiloxane layers are also characterized by a greater diffusion seal. In a particularly expedient embodiment, the at least one organosilicon compound, in particular hexamethyldisiloxane, and the at least one reactive gas, in particular oxygen or air, can be used as a mixture for the treatment step. The previously described embodiment of the use of reactive gases in the, in particular plasma-generated, production of the polysiloxane layer is preferably used in at least one step of the treatment with at least one organosilicon compound, in particular by means of plasma polymerisation, with the formation of a polysiloxane layer or also in every step for the production of a polysiloxane layer Mission. This process variant is particularly preferably used in the production of coated non-metallic substrates, in particular plastic substrates, in process step m) and in the production of coated metallic substrates in process step S). In the method steps n) or T) following the method steps mentioned, the plasma treatment is preferably formed with the aid of a plasma gas from an inert gas, in particular argon, and oxygen or air or nitrogen, in particular oxygen, or with the aid of a plasma gas formed from oxygen, air or nitrogen carried out. This procedure also contributes again to improved adhesion of the overall system, including the top layer.

There are basically several process variants to choose from for the step of plasma treatment with the plasma generator. According to a first variant, the plasma can be formed using at least one inert gas, in particular argon. Alternatively, mixtures of at least one inert gas, in particular argon, and a reactive gas such as oxygen, nitrogen, carbon dioxide, hydrogen, carbon monoxide, hydrogen peroxide gas, water vapor, ozone and/or air can also be used to generate a suitable plasma. Oxygen and nitrogen, in particular oxygen, are preferably used here. Finally, it is also possible to use only reactive gases such as oxygen, nitrogen, hydrogen, carbon dioxide, carbon monoxide, hydrogen peroxide gas, water vapor, ozone and/or air for generating the plasma without using inert gases. Oxygen is preferably used here. With the help of a plasma treatment with the plasma generator, the surface of the substrate to be coated is activated. In a plasma process, a high-energy plasma regularly acts on the surface of the molded part, so that active centers are formed on this surface. These can be, for example, hydroxyl groups and/or carbonyl groups. In the same way, activation of the surface of the substrate surface to be coated can take place by means of flaming. In a preferred embodiment, a volatile silane or a compound containing titanium and aluminum can be added to a flame, for example a propane gas flame, which burns in an air atmosphere. The surface of the substrate, in particular a plastic substrate, can be changed by the flame treatment in a manner similar to that in the plasma process, for example with the formation of hydroxyl groups.

The methods described here offer the great advantage that almost all method steps can be carried out in the application system for the application of a metal layer. In addition to the application of the metal layers, this also applies to the activation of surfaces by means of plasma treatment with the plasma generator and the application of the polysiloxane layer, in particular by means of plasma polymerisation. Only the cleaning steps, the application of a primer layer, the application of a conversion layer and the application of the top layer are regularly applied outside of the application system mentioned. Accordingly, it can be provided that the, in particular each, plasma treatment with the plasma generator and/or the, in particular each, application of the metal layer and/or the, in particular each, application of the polysiloxane layer in the application system for the application of a metal layer, in particular in the vacuum vapor deposition system or in the sputtering system , is carried out and/or that the application of the primer layer and/or the application of the conversion layer and/or the application of the cover layer is carried out outside of the application system for the application of a metal layer, in particular the vacuum vapor deposition system or the sputter system.

Water-dilutable coating compositions can also be used for the top layer, for example. The top layer can be formed from polyacrylate resins, polyester resins, amino resins or polyurethane compounds. In the methods described herein, top layers which are based on a UV-curing coating material are preferably applied. Accordingly, a preferred topcoat is a UV-cured topcoat. The topcoat can be obtained, for example, via a clear coat or a transparent powder. The top layer is preferably applied using a wet paint process or a powder coating process. Accordingly, the top coat can be, for example, one-, two- or multi-component paints, with clear paints being preferred. These clear coats can be, for example, chemically crosslinking two-component, one-component, heat-curing or UV-curing coatings. Furthermore, 1K or 2K stove enamel can be used for the top layer.

The cover layer generally has a thickness in the range from 10 to 50 μm, preferably in the range from 20 to 30 μm. It is essential for the methods described herein that the material forming the cover layer is applied to a polysiloxane layer previously activated by means of plasma treatment and/or corona treatment, which in turn was preferably obtained by means of plasma polymerisation, preferably essentially without a time delay.

The plasma treatment with the plasma generator is sometimes also described with the term smoldering.

For the application of the metal layers, for example, the techniques of physical vapor deposition (PVD), chemical vapor deposition (CVD), evaporation using an electron beam evaporator, evaporation using a resistance evaporator, induction evaporation, ARC evaporation or the cathode or anode sputtering (sputter coating). Accordingly, suitable application systems for the application of a metal layer are, for example, preferably vacuum vapor deposition systems or sputter systems. Suitable vacuum evaporation systems suitably include PVD systems (Physical Vapor Deposition), CVD systems (Chemical Vapor Deposition), electron beam evaporators, resistance evaporators, induction evaporators and ARC evaporators. Suitable sputtering equipment includes, for example, cathode atomizers and anode atomizers. As is known to those skilled in the art, a metal layer consists primarily of metal. This does not completely rule out additives such as those used in stainless steel in the form of carbon. The metal content of the present metal layer is preferably greater than 90% by weight, in particular 95% by weight and very particularly preferably ≧98% by weight.

The metal layer is preferably a vapor-deposited or sputtered-on metal layer, in particular a PVD metal layer. Resistance-heated metal coil or metal boat evaporators are generally used in the PVD process, with tungsten coils of various shapes being preferred. In the PVD process, an evaporator is generally equipped with coils that can be clamped onto evaporator rails that are insulated from one another. A precisely determined quantity of metal to be vapor-deposited is preferably placed in each coil. After closing and evacuating the PVD system, the evaporation can be started by switching on the power supply, which causes the evaporator bars to glow the coils. The solid metal begins to melt and completely wets the mostly twisted coils. By adding more energy, the liquid metal is converted into the gas phase so that it can be deposited on the substrate to be coated. The thickness of the metal layer and thus also the appearance of the same can be adjusted in a targeted manner via the amount of metal transferred into the gas phase and/or the duration of the coating phase.

Another preferred method for depositing the metal layer on the substrate is cathode sputtering (sputtering method). A cathode is placed in an evacuated container and is connected to the negative pole of a power supply. The coating material to be sputtered is mounted immediately in front of the cathode and the substrates to be coated are placed opposite the coating material to be sputtered. Furthermore, argon can be passed through the container as a process gas, which finally also has an anode which is connected to the positive pole of a power supply. After the container has been pre-evacuated, the cathode and anode are connected to the power supply. The mean free path length of the charge carriers is significantly reduced by the targeted and controlled admission of argon. Argon atoms are ionized in the electric field between cathode and anode. The positively charged particles are accelerated towards the negatively charged cathode with high energy. Upon impact and particle collisions in the coating material, this is converted into the vapor phase, accelerated into free space with high energy and then condenses on the substrates to be coated. Different metal layer thicknesses can be specifically adjusted with the sputtering process.

The metal layers obtainable with the methods and systems mentioned preferably have an average, in particular absolute, thickness in the range from 1 nm to 150 nm, in particular in the range from 5 nm to 120 nm Example with a thickness in the range of 60 nm to 120 nm, preferably set with a thickness in the range of 75 nm to 110 nm. With these thicknesses, the metal layer, in particular the aluminum layer, is covering, i.e. essentially not transparent or translucent on the surface. In this way, high-gloss layers can be obtained.

Coloring of the coating present on the non-metallic and metallic substrates can also be accomplished using the methods described herein by using a coating material containing at least one colorant, for example at least one pigment and/or at least one dye, for the application of the top layer. is used. Glazes known to those skilled in the art can also be used to color the top layer, for example to obtain brass, titanium and gold tones or individual color tones such as red, blue, yellow, green, etc. or anodized color tones. For example, effect pigments such as pearlescent pigments, LCP pigments (liquid crystal polymer) or OV pigments (optically variable) can also be incorporated into the top layer.

For the production of the coated non-metallic and metallic substrates according to the invention, an application system for the application of a metal layer can be used, comprising or representing a vacuum vapor deposition system with a vacuum chamber, and at least one, in particular a large number of first heatable receiving units, in particular shells, boats or coils , each in operative connection with a first heating device or comprising or representing a first heating device, each designed and suitable for receiving a first metal or a first metal alloy with a first melting point or melting range, and at least one, in particular a large number of second heatable receiving units, in particular Shells, boats or coils, each in operative connection with a second heating device or comprising or representing a second heating device, each designed and suitable for receiving a second meta lls or second metal alloy with a second melting point or melting range, the first melting point or the first melting range being different from the second melting point or second melting range, and also a control device for setting the first and second temperatures in such a way that the first and evaporate (co-evaporate) the second metal or the first and second metal alloy essentially at the same time or with a temporal overlap.

In one embodiment variant, it can be provided that the application system for the application of a metal layer has at least a first container, in particular outside the vacuum chamber of the vacuum vapor deposition system, for receiving a first organosilicon compound with a feed line to the vacuum chamber and at least a second container, in particular outside the vacuum chamber of the vacuum vapor deposition system present container for receiving a second organosilicon compound with a line to the vacuum chamber.

It has proven to be particularly expedient to also equip the disclosed application system for the application of a metal layer with at least one frame, in particular in the vacuum chamber, with a longitudinal orientation and with at least one carrier, in particular in the form of a shaft, which is essentially along the longitudinal orientation of the frame, designed and set up to receive at least one, in particular a multiplicity of non-metallic and/or metallic substrates, wherein the frame and/or the at least one carrier rotates about an axis, in particular a substantially horizontally aligned axis. Suitable frames that can be used with the application system according to the invention are, for example EP 2 412 445 and the DE 20 2007 016 072 refer to.

The non-metallic and metallic substrates obtainable by the process according to the invention can be used, for example, as accessories for automobile construction, motorcycle construction, bicycle construction or shipbuilding, for rims, in particular light metal rims, wheels, in particular light metal wheels, or as a component thereof, for sanitary fittings, in particular as Annatur , or as a component thereof, for interior or exterior body parts or as a component thereof, for handles or handle components, in particular door handles or as a component thereof, for profiles or frames, in particular window frames or as a component thereof, for fitting systems or as a component thereof, in particular signs and doorplates, for casings or as packaging or as a component thereof, for interior or exterior components of ships or as a component thereof, for ornaments or as a component thereof, for precious components or as a component thereof, for interior or outdoor furniture or components thereof, for household appliances, in particular coffee machines, or components thereof, for internal or external components of aircraft or as a component thereof, for internal or external components of buildings or as a component thereof, for radiators or pipes or as a component thereof, for elevator components or as a component thereof, for Components of electronic components or devices or as a part thereof, for components of kitchen appliances, for example coffee machines, or as a component of communication components or devices, in particular mobile phones, or as a part thereof.

The invention is based on the surprising finding that the substrates obtainable by the processes described herein provide a high-quality gloss coating which permanently retains its gloss. In addition, it was surprisingly found that the coated non-metallic and metallic substrates obtainable by the process described herein are endowed with outstanding corrosion resistance. The coated substrates obtainable by the processes described herein are also distinguished by pronounced adhesion. Accordingly, these coated substrates show outstanding resistance to corrosion even when the surfaces have suffered mechanical damage, for example from stone chipping or scratching. A further advantage associated with the methods described here and with the application system described here is that only very short changeover times are required to coat new substrate batches. In addition, the method described here makes it possible to significantly reduce the scope of the overall system for producing coated substrates, starting from the substrate to be coated that has not yet been cleaned, so that there is a significantly reduced space requirement compared to conventional systems. In addition, it is possible with the methods described here to reduce the processing time up to the completion of the coated, ready-to-sell substrate considerably. This is inevitably accompanied by reduced cycle times.

The features of the invention disclosed in the above description and in the claims can be essential both individually and in any combination for the realization of the invention in its various embodiments.

Claims (15)

1. Coated non-metal substrate obtained or obtainable according to a method comprising the steps

   a) providing a non-metal substrate with at least one surface which can be coated at least in certain areas,

   b) providing an application system for applying a metal layer,

   c) providing at least one plasma generator and/or at least one corona system,

   d) optionally, plasma treatment using the plasma generator and/or corona treatment of the non-metal substrate or the coatable surface of the non-metal substrate,

   e) optionally, treating the non-metal substrate obtained according to step a) or d) or the coatable surface of the non-metal substrate with at least one organosilicon compound by means of plasma polymerization such that a polysiloxane layer is formed,

   f) optionally, plasma treatment using the plasma generator and/or corona treatment of the polysiloxane layer according to step e),

   g) optionally, applying at least one priming coat to the non-metal substrate or the coatable surface of the non-metal substrate according to step a) or d) or to the polysiloxane layer according to step e) or f),

   h) optionally, plasma treatment using the plasma generator and/or corona treatment of the priming coat according to step g),

   i) treating the non-metal substrate or the coatable surface of the non-metal substrate according to step a) or d) or the priming coat obtained according to step g) or h) with at least one organosilicon compound by means of plasma polymerization such that a polysiloxane layer is formed,

   j) optionally, plasma treatment using the plasma generator and/or corona treatment of the polysiloxane layer according to step i),

   k) applying at least one metal layer containing or consisting of a first metal selected from the group consisting of aluminium, silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt, nickel, copper, chrome, palladium, molybdenum, tungsten, platinum, titanium, zirconium and zinc or containing or consisting of a first metal alloy selected from the group consisting of brass, bronze, steel, or aluminium, magnesium and titanium alloys, using the application system, in particular by means of vapour deposition and/or sputter technology, to the non-metal substrate or to the coatable surface of the non-metal substrate according to step a) or d) or to the polysiloxane layer according to step e) or f) or to the priming coat according to step g) or h) or to the polysiloxane layer according to step i) or j),

   l) optionally, plasma treatment using the plasma generator and/or corona treatment of the metal layer according to step k),

   m) treating the metal layer obtained according to step k) or 1) with at least one organosilicon compound by means of plasma polymerization such that a polysiloxane layer is formed,

   n) plasma treatment using the plasma generator and/or corona treatment of the polysiloxane layer according to step m), and

   o) applying a cover layer to the treated polysiloxane layer according to step n).
2. Non-metal substrate according to Claim 1, characterized in that

   steps g), h), k), m), n) and o) each follow one another, in particular omitting steps d), e) and/or f) or using step d) and omitting step e) and f), or

   that steps g), h), i), k), m), n) and o) each follow one another, in particular omitting steps d), e) and/or f) or using step d) and omitting step e) and f), or

   that steps d), e), f), k), m), n) and o) each follow one another or

   that steps d), e), f), i), k), m), n) and o) each follow one another or

   that steps d), e), f), g), k), m), n) and o) each follow one another or

   that steps d), e), f), g), i), k), m), n) and o) each follow one another.
3. Coated metal substrate obtained or obtainable according to a method comprising the steps

   A) providing a metal substrate with at least one surface which can be coated at least in certain areas,

   B) providing an application system for applying a metal layer,

   C) providing at least one plasma generator and/or at least one corona system,

   D) optionally, cleaning the metal substrate or the coatable surface of the metal substrate,

   E) optionally, applying at least one metal layer containing or consisting of a second metal selected from the group consisting of titanium, hafnium and zirconium, or a second metal alloy selected from the group consisting of titanium, hafnium and zirconium alloys, using the application system, to the metal substrate or the coatable surface of the metal substrate according to step A) or D),

   F) optionally, plasma treatment using the plasma generator and/or corona treatment of the metal substrate or the coatable surface of the metal substrate according to step A) or D) or of the metal layer according to step E),

   G) optionally, treating the metal substrate obtained according to step A) or D) or treating the coatable surface of the metal substrate obtained according to step A) or D) or the metal layer obtained according to step E) or F) with at least one organosilicon compound by means of plasma polymerization such that a polysiloxane layer is formed,

   H) optionally, plasma treatment using the plasma generator and/or corona treatment of the polysiloxane layer according to step G),

   I) optionally, applying a conversion layer to the metal substrate or the coatable surface of the metal substrate according to step A) or D) or to the metal layer according to step E) or F) or to the polysiloxane layer according to step G) or H),

   J) optionally, plasma treatment using the plasma generator and/or corona treatment of the conversion layer according to step 1),

   K) optionally, treating the conversion layer obtained according to step I) or J) with at least one organosilicon compound by means of plasma polymerization such that a polysiloxane layer is formed,

   L) optionally, plasma treatment using the plasma generator and/or corona treatment of the treated polysiloxane layer obtained according to step K),

   M) optionally, applying at least one priming coat to the metal substrate or the coatable surface of the metal substrate according to step A) or D) or to the metal layer according to step E) or F) or to the polysiloxane layer according to step G) or H) or to the conversion layer according to step I) or J) or to the polysiloxane layer according to step K) or L),

   N) optionally, plasma treatment using the plasma generator and/or corona treatment of the priming coat according to step M),

   O) treating the metal substrate or the coatable surface of the metal substrate according to step A) or D) or the metal layer obtained according to step E) or F) or the conversion layer according to step I) or J) or the priming coat obtained according to step M) or N) with at least one organosilicon compound by means of plasma polymerization such that a polysiloxane layer is formed,

   P) optionally, plasma treatment using the plasma generator and/or corona treatment of the treated polysiloxane layer obtained according to step O),

   Q) applying at least one metal layer containing or consisting of a first metal selected from the group consisting of aluminium, silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt, molybdenum, tungsten, nickel, copper, chrome, palladium, platinum, titanium, zirconium and zinc or containing or consisting of a first metal alloy selected from the group consisting of brass, bronze, steel or aluminium, magnesium and titanium alloys, using the application system, to the metal substrate or the coatable surface of the metal substrate according to step A) or D) or to the metal layer according to step E) or F) or to the polysiloxane layer according to step G) or H) or to the conversion layer according to step I) or J) or to the polysiloxane layer according to step K) or L) or to the priming coat according to step M) or N) or to the polysiloxane layer according to step O) or P),

   R) optionally, plasma treatment using the plasma generator and/or corona treatment of the metal layer according to step Q),

   S) treating the metal layer obtained according to step Q) or R) with at least one organosilicon compound by means of plasma polymerization such that a polysiloxane layer is formed,

   T) plasma treatment using the plasma generator and/or corona treatment of the polysiloxane layer according to step S), and

   U) applying an cover layer to the treated polysiloxane layer according to step T).
4. Metal substrate according to Claim 3, characterized in that

   steps D), M), N), Q), S), T) and U) each follow one another or

   that steps D), M), N), O), Q), S), T) and U) each follow one another or

   that steps D), E), F,), M), Q), S), T) and U) each follow one another or

   that steps D), E), F,), M), O), Q), S), T) and U) each follow one another or

   that steps D), G), H), M), Q), S), T) and U) each follow one another or

   that steps D), G), H), M), O), Q), S), T) and U) each follow one another or

   that steps D), E), G), H), M), Q), S), T) and U) each follow one another or

   that steps D), E), G), H), M), O), Q), S), T) and U) each follow one another or

   that steps D), M), Q), S), T) and U) each follow one another or

   that steps D), M), O), Q), S), T) and U) each follow one another or

   that steps D), G), H), Q), S), T) and U) each follow one another or

   that steps D), G), H), O), Q), S), T) and U) each follow one another.
5. Non-metal substrate according to Claim 1 or 2 or metal substrate according to Claim 3 or 4, characterized in that the non-metal substrate comprises glass, ceramic, composite fibre materials, carbon materials, plastic or wood or consists thereof, or that the metal substrate comprises metals or metal alloys or consists thereof.
6. Metal substrate according to Claim 3 or 4 or according to Claim 5, if and when reference is made back directly or indirectly to Claim 3 or 4,
   characterized in that
   the metal substrate is selected from the group consisting of aluminium, aluminium alloys, iron, iron alloys, in particular steel or stainless steel, copper, copper alloys, titanium, titanium alloys, zinc, zinc alloys, nickel, nickel alloys, molybdenum, molybdenum alloys, magnesium, magnesium alloys, lead, lead alloys, tungsten, tungsten alloys, manganese, manganese alloys, brass, bronze, die-cast nickel, die-cast zinc and die-cast aluminium or any mixtures thereof.
7. Non-metal substrate according to Claim 1 or 2 or according to Claim 5, if and when reference is made back directly or indirectly to Claim 1 or 2, or metal substrate according to Claim 3 or 4 or according to Claim 5 or 6, if and when reference is made back directly or indirectly to Claim 3 or 4, characterized in that the organosilicon compound comprises at least one amino-containing silane, in particular aminopropyltriethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane or any mixtures thereof.
8. Non-metal substrate according to Claim 1 or 2 or according to Claim 5 or 7, if and when reference is made back directly or indirectly to Claim 1 or 2, or metal substrate according to Claim 3 or 4 or according to any one of Claims 5 to 7, if and when reference is made back directly or indirectly to Claim 3 or 4, characterized in that the cover layer comprises polyacrylate resins, polyester resins, aminoplast resins or polyurethane compounds or consists thereof, and/or that the cover layer is formed from a UV-curable coating material or from a 1K or 2K stove enamel, in particular constitutes a UV-curable cover layer or a 1K or 2K stove enamel cover layer.
9. Non-metal substrate according to Claim 1 or 2 or according to any one of Claims 5, 7 or 8, if and when reference is made back directly or indirectly to Claim 1 or 2, or metal substrate according to Claim 3 or 4 or according to any one of Claims 5 to 8, if and when reference is made back directly or indirectly to Claim 3 or 4, characterized in that
   the metal layer is applied by means of physical vapour deposition (PVD), chemical vapour deposition (CVD), vapour deposition using an electron beam vaporizer, vapour deposition using a resistance vaporizer, induction vaporization, ARC vaporization or cathode or anode spraying (sputter coating).
10. Non-metal substrate according to Claim 1 or 2 or according to any one of Claims 5 or 7 to 9, if and when reference is made back directly or indirectly to Claim 1 or 2, or metal substrate according to Claim 3 or 4 or according to any one of Claims 5 to 9, if and when reference is made back directly or indirectly to Claim 3 or 4, characterized in that
    during the step of applying the metal layer a first metal, in particular aluminium, or a first metal alloy, in particular aluminium alloy, is coevaporated in the application system, in particular the vacuum vapour deposition system or sputter system, for applying a metal layer with a second metal, in particular selected from the group consisting of titanium, zirconium and hafnium, in particular zirconium or with a second metal alloy, in particular selected from the group consisting of titanium, zirconium and hafnium alloys, such that these overlap in time.
11. Non-metal substrate according to Claim 1 or 2 or according to any one of Claims 5 or 7 to 10, if and when reference is made back directly or indirectly to Claim 1 or 2, or metal substrate according to Claim 3 or 4 or according to any one of Claims 5 to 10, if and when reference is made back directly or indirectly to Claim 3 or 4, characterized in that
    at least one colorant, in particular pigment, is introduced into the application system, in particular in form of a mixture, for applying a metal layer together with the at least one organosilicon compound, in particular for the plasma polymerization, and/or that a coating material containing at least one colorant, in particular one pigment, is used for applying the cover layer.
12. Non-metal substrate according to Claim 1 or 2 or according to any one of Claims 5 or 7 to 11, if and when reference is made back directly or indirectly to Claim 1 or 2, or metal substrate according to Claim 3 or 4 or according to any one of Claims 5 to 11, if and when reference is made back directly or indirectly to Claim 3 or 4, characterized in that
    the step involving treatment with at least one organosilicon compound by means of plasma polymerization such that a polysiloxane layer is formed is performed in the presence of at least one reactive gas such as oxygen, nitrogen, carbon dioxide, hydrogen, carbon monoxide, hydrogen peroxide gas, water vapour, ozone and/or air, in particular in the presence of oxygen or air.
13. Non-metal substrate or metal substrate according to Claim 12, characterized in that the at least one organosilicon compound, in particular hexamethyldisiloxane, and the at least one reactive gas, in particular oxygen or air, are used as a mixture for the treatment step.
14. Non-metal substrate according to Claim 1 or 2 or according to any one of Claims 5 or 7 to 13, if and when reference is made back directly or indirectly to Claim 1 or 2, or metal substrate according to Claim 3 or 4 or according to any one of Claims 5 to 13, if and when reference is made back directly or indirectly to Claim 3 or 4, characterized in that
    the step involving treatment with at least one organosilicon compound by means of plasma polymerization such that a polysiloxane layer is formed in the presence of at least one reactive gas is used at least for one step for manufacturing a polysiloxane layer or for each step for manufacturing a polysiloxane layer, in particular for step m) or for step S).
15. Use of the non-metal substrate according to Claim 1 or 2 or according to any one of Claims 5 or 7 to 14, if and when reference is made back directly or indirectly to Claim 1 or 2, or of the metal substrate according to Claim 3 or 4 or according to any one of Claims 5 to 14, if and when reference is made back directly or indirectly to Claim 3 or 4, as as accessories for automobile manufacture, motorcycle manufacture, bicycle manufacture or shipbuilding, for rims, in particular light metal alloy rims, wheels, in particular light metal alloy wheels, or as a constituent part thereof, for sanitary installation objects, in particular as a tap or mixer, or as a constituent part thereof, for automobile body internal or external components or as a constituent part thereof, for handles or handle components, in particular door handles, or as a constituent part thereof, for profiles or frames, in particular window frames, or as a constituent part thereof, for fittings systems or as a constituent part thereof, in particular signs and door signs, for housings or as packing, or as a constituent part thereof, for internal or external components of ships, or as a constituent part thereof, for domestic appliances, in particular coffee-making machines, or as a constituent part thereof, for j ewelry items, or as a constituent part thereof, for high-quality structural components or as a constituent part thereof, for indoor or outdoor furniture items, or for constituent parts thereof, for internal or external components of aircraft or as a constituent part thereof, for internal or external components of buildings or as a constituent part thereof, for heating elements or pipes, or as a constituent part thereof, for elevator components or as a constituent part thereof, for parts of electronic components or devices, or as a constituent part thereof, for components of kitchen appliances, for example coffee-making machines, or as a part of communications components or devices, in particular mobile telephones, or as a constituent part thereof.